Liquid crystal composition and liquid crystal display device

ABSTRACT

To provide a liquid crystal composition satisfying at least one of characteristics such as high maximum temperature of a nematic phase, low minimum temperature thereof, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy and specific resistance, high stability to ultraviolet light and heat; a liquid crystal composition having a suitable balance regarding at least two thereof; and an AM device having short response time, large voltage holding ratio and contrast ratio, long life and so forth. The liquid crystal composition has nematic phase, and contains as a first component a specific compound having large dielectric anisotropy and as a second component a specific compound having small viscosity, and may contain as a third component a specific compound having high maximum temperature or large dielectric anisotropy, and as a fourth component a specific compound having high maximum temperature or small viscosity, and a liquid crystal display device includes the composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the priority benefit of Japan application serial no. 2012-181176, filed on Aug. 17, 2012. The entirety of the above-mentioned patent application is hereby incorporated by reference herein and made a part of this specification.

TECHNICAL FIELD

The invention relates to a liquid crystal composition mainly suitable for use in an active matrix (AM) device and so forth, and an AM device and so forth including the composition. In particular, the invention relates to a liquid crystal composition having a positive dielectric anisotropy, and a device and so forth that include the composition and have a twisted nematic (TN) mode, an optically compensated bend (OCB) mode, an in-plane switching (IPS) mode, a fringe field switching (FFS) mode, a polymer sustained alignment mode (PSA) or a field-induced photo-reactive alignment (FPA) mode.

BACKGROUND ART

In a liquid crystal display device, a classification based on an operating mode for liquid crystals includes a phase change (PC) mode, a twisted nematic (TN) mode, a super twisted nematic (STN) mode, an electrically controlled birefringence (ECB) mode, an optically compensated bend (OCB) mode, an in-plane switching (IPS) mode, a vertical alignment (VA) mode, a fringe field switching (FFS) mode, a polymer sustained alignment (PSA) mode and a field-induced photo-reactive alignment (FPA) mode. A classification based on a driving mode in the device includes a passive matrix (PM) and an active matrix (AM). The PM is classified into static, multiplex and so forth, and the AM is classified into a thin film transistor (TFT), a metal insulator metal (MIM) and so forth. The TFT is further classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to a production process. A classification based on a light source includes a reflective type utilizing natural light, a transmissive type utilizing backlight and a transflective type utilizing both the natural light and the backlight.

The devices include a liquid crystal composition having suitable characteristics. The liquid crystal composition has a nematic phase. General characteristics of the composition should be improved to obtain an AM device having good general characteristics. Table 1 below summarizes a relationship of the general characteristics between two aspects. The general characteristics of the composition will be further explained based on a commercially available AM device. A temperature range of the nematic phase relates to a temperature range in which the device can be used. A preferred maximum temperature of the nematic phase is approximately 70° C. or higher and a preferred minimum temperature of the nematic phase is approximately −10° C. or lower. Viscosity of the composition relates to a response time in the device. A short response time is preferred for displaying moving images on the device. Accordingly, a small viscosity in the composition is preferred. A small viscosity at a low temperature is further preferred. An elastic constant of the composition relates to contrast of the device. For increasing the contrast in the device, a large elastic constant in the composition is further preferred.

TABLE 1 General Characteristics of Composition and AM Device General Characteristics of General Characteristics of No. Composition AM Device 1 Wide temperature range of Wide usable temperature range a nematic phase 2 Small viscosity ¹⁾ Short response time 3 Suitable optical anisotropy Large contrast ratio 4 Large positive or negative Low threshold voltage and small dielectric anisotropy electric power consumption Large contrast ratio 5 Large specific resistance Large voltage holding ratio and large contrast ratio 6 High stability to ultraviolet Long service life light and heat 7 Large elastic constant Large contrast ratio and short response time ¹⁾ A liquid crystal composition can be injected into a liquid crystal cell in a shorter period of time.

An optical anisotropy of the composition relates to a contrast ratio in the device. A product (Δn×d) of the optical anisotropy (Δn) of the composition and a cell gap (d) in the device is designed so as to maximize the contrast ratio. A suitable value of the product depends on a type of the operating mode. In a device of a mode such as TN, a suitable value is approximately 0.45 micrometer. In the above case, a composition having a large optical anisotropy is preferred for a device having a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small electric power consumption and a large contrast ratio in the device. Accordingly, the large dielectric anisotropy is preferred. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Accordingly, a composition having a large specific resistance at room temperature and also at a temperature close to a maximum temperature of the nematic phase in an initial stage is preferred. A composition having a large specific resistance at room temperature and also at a temperature close to the maximum temperature of the nematic phase even after the device has been used for a long period of time is preferred. Stability of the composition to ultraviolet light and heat relates to a service life of the liquid crystal display device. In the case where the stability is high, the device has a long service life. Such characteristics are preferred for an AM device for use in a liquid crystal projector, a liquid crystal television and so forth. A large elastic constant in the composition contributes to a large contrast ratio and a short response time in the device. Accordingly, the large elastic constant is preferred.

A composition having a positive dielectric anisotropy is used for an AM device having the TN mode. On the other hand, a composition having a negative dielectric anisotropy is used for an AM device having the VA mode. A composition having a positive or negative dielectric anisotropy is used for an AM device having the IPS mode or the FFS mode. A composition having a positive or negative dielectric anisotropy is used for an AM device having the PSA mode or the FPA mode. An example of the liquid crystal composition having the positive dielectric anisotropy is disclosed in Patent literature No. 1 as described below.

CITATION LIST Patent Literature

-   Patent literature No. 1: JP 2005-298466 A.

A desirable AM device has characteristics such as a wide temperature range in which a device can be used, a short response time, a large contrast ratio, a low threshold voltage, a large voltage holding ratio and a long service life. A shorter response time even by one millisecond is desirable. Thus, desirable characteristics of a composition include a high maximum temperature of a nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat and a large elastic constant.

SUMMARY OF INVENTION Solution to Problem

The invention concerns a liquid crystal composition that has a nematic phase and contains at least one compound selected from the group of compounds represented by formula (1) as a first component and at least one compound selected from the group of compounds represented by formula (2) as a second component, and concerns a liquid crystal display device including the composition:

wherein, R¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine; R² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; R³ is alkenyl having 2 to 12 carbons, or —CH═CF₂; ring A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; ring B is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z¹ is independently a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; and m is 1, 2 or 3.

The invention also concerns use of the composition in a liquid crystal display device.

DESCRIPTION OF EMBODIMENTS Technical Problem

One of the aims of the invention is to provide a liquid crystal composition satisfying at least one of characteristics such as a high maximum temperature of a nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light, a high stability to heat and a large elastic constant. Another aim is to provide a liquid crystal composition having a suitable balance regarding at least two of the characteristics. A further aim is to provide a liquid crystal display device including such a composition. An additional aim is to provide a composition having a suitable optical anisotropy, a large dielectric anisotropy, a high stability to ultraviolet light, a large elastic constant and so forth, and is to provide an AM device having a short response time, a large voltage holding ratio, a large contrast ratio, a long service life and so forth.

Advantageous Effects of Invention

An advantage of the invention is a liquid crystal composition satisfying at least one of characteristics such as a high maximum temperature of a nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a high stability to ultraviolet light and a high stability to heat. One aspect of the invention is a liquid crystal composition having a suitable balance regarding at least two of the characteristics. Another aspect is a liquid crystal display device including such a composition. A further aspect is a composition having a suitable optical anisotropy, a large dielectric anisotropy, a high stability to ultraviolet light and so forth, and is an AM device having a short response time, a large voltage holding ratio, a large contrast ratio, a long service life and so forth.

Usage of terms herein is as described below. A liquid crystal composition or a liquid crystal display device of the invention may be occasionally abbreviated as “composition” or “device,” respectively. The liquid crystal display device is a generic term for a liquid crystal display panel and a liquid crystal display module. “Liquid crystal compound” means a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase but being useful as a component of the composition. Such a useful compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and a rod-like molecular structure. An optically active compound or a polymerizable compound may be occasionally added to the composition. Even in the case where the compounds are liquid crystalline, the compounds are classified as an additive herein. At least one compound selected from the group of compounds represented by formula (1) may be occasionally abbreviated as “compound (1).” “Compound (1)” means one compound or two or more compounds represented by formula (1). A same rule applies to any other compound represented by any other formula. “At least one” in the context of “replaced” means that not only positions but also numbers may be selected without limitation.

A higher limit of a temperature range of the nematic phase may be occasionally abbreviated as “maximum temperature.” A lower limit of the temperature range of the nematic phase may be occasionally abbreviated as “minimum temperature.” An expression “having a large specific resistance” means that the composition has a large specific resistance at room temperature and also at a temperature close to the maximum temperature of the nematic phase in an initial stage, and that the composition has a large specific resistance at room temperature and also at a temperature close to the maximum temperature of the nematic phase even after the device has been used for a long period of time. An expression “having a large voltage holding ratio” means that the device has a large voltage holding ratio at room temperature and also at a temperature close to the maximum temperature of the nematic phase in an initial stage, and that the device has a large voltage holding ratio at room temperature and also at a temperature close to the maximum temperature of the nematic phase even after the device has been used for a long period of time. When characteristics such as an optical anisotropy are explained, values obtained according to the measuring methods described in Examples will be used. A first component includes one compound or two or more compounds. “Ratio of the first component” is expressed in terms of weight percent (% by weight) of the first component based on the total weight of the liquid crystal composition. A ratio of a second component and so forth are also expressed in a similar way. A ratio of the additive mixed with the composition is expressed in terms of weight percent (% by weight) or weight parts per million (ppm) based on the total weight of the liquid crystal composition.

A symbol R¹ is used for a plurality of compounds in chemical formulas of component compounds. Groups selected by R¹ may be identical or different in two of arbitrary compounds among the plurality of compounds. In one case, for example, R¹ of compound (1) is ethyl and R¹ of compound (1-1) is ethyl. In another case, R¹ of compound (1) is ethyl and R¹ of compound (1-1) is propyl. A same rule also applies to a symbol R⁴, X¹ or the like.

The invention includes the items described below.

Item 1. A liquid crystal composition that has a nematic phase and contains at least one compound selected from the group of compounds represented by formula (1) as a first component and at least one compound selected from the group of compounds represented by formula (2) as a second component:

wherein, R¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine; R² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; R³ is alkenyl having 2 to 12 carbons, or —CH═CF₂; ring A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; ring B is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z¹ is independently a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; and m is 1, 2 or 3.

Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-3) as the first component:

wherein, R¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine.

Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from the group of compounds represented by formula (1-1) according to item 2 as the first component.

Item 4. The liquid crystal composition according to any one of items 1 to 3, containing at least one compound selected from the group of compounds represented by formula (1-2) according to item 2 as the first component.

Item 5. The liquid crystal composition according to any one of items 1 to 4, wherein a ratio of the first component is in the range of 5% by weight to 30% by weight and a ratio of the second component is in the range of 10% by weight to 95% by weight, based on the total weight of the liquid crystal composition.

Item 6. The liquid crystal composition according to any one of items 1 to 5, further containing at least one compound selected from the group of compounds represented by formula (3) as a third component:

wherein, R⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or an alkenyl having 2 to 12 carbons; ring C is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; X¹ and X² are independently hydrogen or fluorine; Y¹ is fluorine, chlorine, trifluoromethyl or trifluoromethoxy; Z² is independently a single bond, ethylene, carbonyloxy or difluoromethyleneoxy; and n is 1, 2 or 3.

Item 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-18) as the third component:

wherein, R⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons; X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ are independently hydrogen or fluorine; and Y¹ is fluorine, chlorine, trifluoromethyl or trifluoromethoxy.

Item 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the group of compounds represented by formula (3-3) according to item 7 as the third component.

Item 9. The liquid crystal composition according to any one of items 1 to 8, containing at least one compound selected from the group of compounds represented by formula (3-10) according to item 7 as the third component.

Item 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from the group of compounds represented by formula (3-17) according to item 7 as the third component.

Item 11. The liquid crystal composition according to any one of items 6 to 10, wherein a ratio of the third component is in the range of 10% by weight to 85% by weight based on the total weight of the liquid crystal composition.

Item 12. The liquid crystal composition according to any one of items 1 to 11, further containing at least one compound selected from the group of compounds represented by formula (4) as a fourth component:

wherein, R⁵ and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine; ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene; Z³ is independently a single bond, ethylene or carbonyloxy; p is 1, 2 or 3; and ring E when p is 1 is 1,4-phenylene.

Item 13. The liquid crystal composition according to any one of items 1 to 12, containing at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-12) as the fourth component:

wherein, R⁵ and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine.

Item 14. The liquid crystal composition according to any one of items 1 to 13, containing at least one compound selected from the group of compounds represented by formula (4-4) according to item 13 as the fourth component.

Item 15. The liquid crystal composition according to any one of items 1 to 14, containing at least one compound selected from the group of compounds represented by formula (4-7) according to item 13 as the fourth component.

Item 16. The liquid crystal composition according to any one of items 12 to 15, wherein a ratio of the fourth component is in the range of 5% by weight to 75% by weight based on the total weight of the liquid crystal composition.

Item 17. The liquid crystal composition according to any one of items 1 to 16, wherein a maximum temperature of a nematic phase is 70° C. or higher, an optical anisotropy (25° C.) at a wavelength of 589 nanometers is 0.07 or more, and a dielectric anisotropy (25° C.) at a frequency of 1 kHz is 2 or more.

Item 18. A liquid crystal display device including the liquid crystal composition according to any one of items 1 to 17.

Item 19. The liquid crystal display device according to item 18, wherein an operating mode in the liquid crystal display device is a TN mode, an ECB mode, an OCB mode, an IPS mode, a PSA mode or an FPA mode, and a driving mode in the liquid crystal display device is an active matrix mode.

Item 20. Use of the liquid crystal composition according to any one of items 1 to 17 in a liquid crystal display device.

The invention further includes the following items: (1) the composition, further containing the optically active compound; (2) the composition, further containing the additive such as an antioxidant, an ultraviolet light absorber, an antifoaming agent, a polymerizable compound or a polymerization initiator; (3) an AM device including the composition; (4) a device including the composition, and having a TN, ECB, OCB, IPS, FFS, PSA or FPA mode; (5) a transmissive device including the composition; (6) use of the composition as the composition having the nematic phase; and (7) use as an optically active composition by adding the optically active compound to the composition.

The composition of the invention will be explained in the following order. First, a constitution of the component compounds in the composition will be explained. Second, main characteristics of the component compounds and main effects of the compounds on the composition will be explained. Third, a combination of components in the composition, a preferred ratio of the component compounds and the basis thereof will be explained. Fourth, a preferred embodiment of the component compounds will be explained. Fifth, specific examples of the component compounds will be shown. Sixth, the additive that may be mixed with the composition will be explained. Seventh, methods for synthesizing the component compounds will be explained. Last, an application of the composition will be explained.

First, the constitution of the component compounds in the composition will be explained. The composition of the invention is classified into composition A and composition B. Composition A may further contain any other liquid crystal compound, the additive, an impurity or the like, in addition to the liquid crystal compound selected from compound (1), compound (2), compound (3) and compound (4). “Any other liquid crystal compound” means a liquid crystal compound different from compound (1), compound (2), compound (3) and compound (4). Such a compound is mixed with the composition for the purpose of further adjusting the characteristics. The additive includes the optically active compound, the antioxidant, the ultraviolet light absorber, a dye, the antifoaming agent, the polymerizable compound and the polymerization initiator. The impurity includes a compound mixed in a process such as preparation of the component compounds. Even in the case where the compound is liquid crystalline, the compound is classified as the impurity herein.

Composition B consists essentially of compounds selected from the group of compound (1), compound (2), compound (3) and compound (4). A term “essentially” means that the composition may contain the additive and the impurity, but does not contain any liquid crystal compound different from the compounds. Composition B has a smaller number of components than composition A has. Composition B is preferred to composition A in view of cost reduction. Composition A is preferred to composition B in view of possibility of further adjusting physical properties by mixing any other liquid crystal compound.

Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be explained. The main characteristics of the component compounds are summarized in Table 2 on the basis of advantageous effects of the invention. In Table 2, a symbol L stands for “large” or “high,” a symbol M stands for “medium,” and a symbol S stands for “small” or “low.” The symbols L, M and S represent classification based on a qualitative comparison among the component compounds, and 0 (zero) means “a value is nearly zero.”

TABLE 2 Characteristics of Compounds Compounds (1) (2) (3) (4) Maximum temperature S to M S to M S to M S to L Viscosity M to L S M to L S to M Optical anisotropy S to M S M to L S to L Dielectric anisotropy L 0 S to L 0 Specific resistance L L L L

Upon mixing the component compounds with the composition, the main effects of the component compounds on the characteristics of the composition are as described below. Compound (1) increases the dielectric anisotropy. Compound (2) decreases the viscosity. Compound (3) increases the dielectric anisotropy and decreases the minimum temperature. Compound (4) increases the maximum temperature or decreases the viscosity.

Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be explained. The combination of components in the composition includes a combination of the first component and the second component, a combination of the first component, the second component and the third component, a combination of the first component, the second component and the fourth component, and a combination of the first component, the second component, the third component and the fourth component. A preferred combination of components in the composition includes the combination of the first component, the second component, the third component and the fourth component.

A preferred ratio of the first component is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 30% by weight or less for decreasing the minimum temperature. A further preferred ratio is in the range of approximately 5% by weight to approximately 25% by weight. A particularly preferred ratio is in the range of approximately 5% by weight to approximately 15% by weight.

A preferred ratio of the second component is approximately 10% by weight or more for decreasing the viscosity, and approximately 95% by weight or less for decreasing the minimum temperature. A further preferred ratio is in the range of approximately 15% by weight to approximately 80% by weight. A particularly preferred ratio is in the range of approximately 15% by weight to approximately 70% by weight.

A preferred ratio of the third component is approximately 10% by weight or more for increasing the dielectric anisotropy, and approximately 85% by weight or less for decreasing the minimum temperature. A further preferred ratio is in the range of approximately 15% by weight to approximately 75% by weight. A particularly preferred ratio is in the range of approximately 15% by weight to approximately 70% by weight.

A preferred ratio of the fourth component is approximately 5% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 75% or less for increasing the dielectric anisotropy. A further preferred ratio is in the range of approximately 5% by weight to approximately 65% by weight. A particularly preferred ratio is in the range of approximately 10% by weight to approximately 60% by weight.

Fourth, the preferred embodiment of the component compounds will be explained. R¹, R⁵, and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine. Preferred R¹, R⁵ or R⁶ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or increasing the stability to heat. R² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. Preferred R² is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or increasing the stability to heat. R³ is alkenyl having 2 to 12 carbons, or —CH═CF₂. Preferred R³ is alkenyl having 2 to 12 carbons for decreasing the viscosity. R⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons. Preferred R⁴ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or increasing the stability to heat.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. Further preferred alkyl is ethyl, propyl, butyl, pentyl or heptyl for decreasing the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. Further preferred alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. Further preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl for decreasing the viscosity. A preferred configuration of —CH═CH— in the alkenyl depends on a position of a double bond. Trans is preferred in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity, for instance. C is preferred in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

Preferred examples of alkenyl in which at least one of hydrogen is replaced by fluorine include 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl and 6,6-difluoro-5-hexenyl. Further preferred examples include 2,2-difluorovinyl and 4,4-difluoro-3-butenyl for decreasing the viscosity.

Alkyl does not include cyclic alkyl. Alkoxy does not include cyclic alkoxy. Alkenyl does not include cyclic alkenyl. With regard to a configuration of 1,4-cyclohexylene, trans is preferred to cis for increasing the maximum temperature.

Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Two of arbitrary ring A when m is 2 or 3 may be identical or different. Preferred ring A is 1,4-cyclohexylene for increasing the maximum temperature, and 1,4-phenylene for increasing the optical anisotropy. Ring B is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Preferred ring B is 1,4-cyclohexylene for increasing the maximum temperature. Ring C is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl. Two of arbitrary ring C when n is 2 or 3 may be identical or different. Preferred ring C is 1,4-cyclohexylene for increasing the maximum temperature, 1,4-phenylene for increasing the optical anisotropy, and 3,5-difluoro-1,4-phenylene for increasing the dielectric anisotropy. Ring D and Ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene, ring E when p is 1 is 1,4-phenylene, and two of arbitrary ring D when p is 2 or 3 may be identical or different. Preferred ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity, and 1,4-phenylene for increasing the optical anisotropy. Then, “2-fluoro-1,4-phenylene” or the like is represented by a ring in which a left-hand side is defined as 1-position to show presence of a difference in positions of fluorine between “2-fluoro-1,4-phenylene” and “3-fluoro-1,4-phenylene.”

Z¹ is a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy, and two of arbitrary Z¹ when m is 2 or 3 may be identical or different. Preferred Z¹ is a single bond for decreasing the viscosity. Z² is a single bond, ethylene, carbonyloxy or difluoromethyleneoxy, and two of arbitrary Z² when n is 2 or 3 may be identical or different. Preferred Z² is a single bond for decreasing the viscosity, and difluoromethyleneoxy for increasing the dielectric anisotropy. Z³ is a single bond, ethylene or carbonyloxy, and two of arbitrary Z³ when p is 2 or 3 may be identical or different. Preferred Z³ is a single bond for decreasing the viscosity, and carbonyloxy for increasing the maximum temperature.

X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ are independently hydrogen or fluorine. Preferred X¹, X², X³, X⁴, X⁵, X⁶, X⁷ or X⁸ is fluorine for increasing the dielectric anisotropy, and hydrogen for decreasing the viscosity.

Y¹ is fluorine, chlorine, trifluoromethyl or trifluoromethoxy. Preferred Y¹ is fluorine for decreasing the viscosity.

Then, m is 1, 2 or 3. Preferred m is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Then, n is 1, 2 or 3. Preferred n is 2 for decreasing the minimum temperature, and 3 for increasing the maximum temperature. Then, p is 1, 2 or 3. Preferred p is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

Fifth, the specific examples of the component compounds will be shown. In preferred compounds described below, R³ is alkenyl having 2 to 12 carbons, or —CH═CF₂, R⁷ is straight-chain alkyl having 1 to 12 carbons or straight-chain alkenyl having 2 to 12 carbons, and R⁸ is straight-chain alkyl having 1 to 12 carbons, straight-chain alkoxy having 1 to 12 carbons or straight-chain alkenyl having 2 to 12 carbons.

Preferred compound (1) includes compound (1-1-1) to compound (1-3-1). Further preferred compound (1) includes compound (1-1-1) and compound (1-2-1). Particularly preferred compound (1) includes compound (1-1-1). Preferred compound (2) includes compound (2-1). Preferred compound (3) includes compound (3-1-1), compound (3-2-1), compound (3-3-1), compound (3-3-2), compound (3-4-1), compound (3-5-1), compound (3-5-2), compound (3-6-1), compound (3-6-2), compound (3-7-1), compound (3-8-1), compound (3-9-1), compound (3-10-1), compound (3-10-2), compound (3-11-1), compound (3-12-1), compound (3-13-1), compound (3-13-2), compound (3-14-1), compound (3-15-1), compound (3-16-1), compound (3-17-1), compound (3-17-2) and compound (3-18-1). Further preferred compound (3) includes compound (3-2-1), compound (3-3-1), compound (3-4-1), compound (3-5-1), compound (3-6-1), compound (3-8-1), compound (3-10-1), compound (3-10-2), compound (3-17-1) and compound (3-17-2). Particularly preferred compound (3) includes compound (3-3-1), compound (3-10-1) and compound (3-17-1). Preferred compound (4) includes compound (4-1-1) to compound (4-12-1). Further preferred compound (4) includes compound (4-4-1) and compound (4-7-1). Particularly preferred compound (4) includes compound (4-4-1).

Sixth, the additive that may be mixed with the composition will be explained. Such an additive includes the optically active compound, the antioxidant, the ultraviolet light absorber, the dye, the antifoaming agent, the polymerizable compound and the polymerization initiator. The optically active compound is mixed with the composition for the purpose of inducing a helical structure in liquid crystals to give a twist angle. Examples of such a compound include compound (5-1) to compound (5-5). A preferred ratio of the optically active compound is approximately 5% by weight or less. A further preferred ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.

The antioxidant is mixed with the composition for the purpose of preventing a decrease in the specific resistance caused by heating in air, or maintaining a large voltage holding ratio at room temperature and also at a temperature close to the maximum temperature of the nematic phase even after the device has been used for a long period of time.

Preferred examples of the antioxidant include compound (6) where q is an integer from 1 to 9. In compound (6), preferred q is 1, 3, 5, 7 or 9. Further preferred q is 1 or 7. Compound (6) where q is 1 is effective in preventing a decrease in the specific resistance caused by heating in air because such compound (6) has a large volatility. Compound (6) where q is 7 is effective in maintaining a large voltage holding ratio at room temperature and also at a temperature close to the maximum temperature of the nematic phase even after the device has been used for a long period of time because such compound (6) has a small volatility. A preferred ratio of the antioxidant is approximately 50 ppm or more for achieving the effect thereof, and approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A further preferred ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet light absorber include a benzophenone derivative, a benzoate derivative and a triazole derivative. A light stabilizer such as an amine having steric hindrance is also preferred. A preferred ratio of the ultraviolet light absorber or the stabilizer is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A further preferred ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

A dichroic dye such as an azo dye or an anthraquinone dye is mixed with the composition to be adapted for a device having a guest host (GH) mode. A preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight. The antifoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is mixed with the composition for preventing foam formation. A preferred ratio of the antifoaming agent is approximately 1 ppm or more for achieving the effect thereof, and approximately 1,000 ppm or less for avoiding a poor display. A further preferred ratio is in the range of approximately 1 ppm to approximately 500 ppm.

The polymerizable compound is mixed with the composition to be adapted for a device having the polymer sustained alignment (PSA) mode. Preferred examples of the polymerizable compound include a compound having a polymerizable group, such as an acrylate, a methacrylate, a vinyl compound, a vinyloxy compound, a propenyl ether, an epoxy compound (oxirane, oxetane) and a vinyl ketone. Particularly preferred examples include an acrylate derivative or a methacrylate derivative. Examples of such a compound include compound (7-1) to compound (7-9). A preferred ratio of the polymerizable compound is approximately 0.05% by weight or more for achieving the effect thereof, and approximately 10% by weight or less for avoiding a poor display. A further preferred ratio is in the range of approximately 0.1% by weight to approximately 2% by weight.

wherein, R⁹, R¹⁰, R¹¹ and R¹² are independently acryloyl or methacryloyl, R¹³ and R¹⁴ are independently hydrogen, halogen or alkyl having 1 to 10 carbons, Z⁴, Z⁵, Z⁶ and Z⁷ are independently a single bond or alkylene having 1 to 12 carbons, in which at least one of —CH₂— may be replaced by —O— or —CH═CH—, and r, s and t are 0, 1 or 2.

The polymerizable compound is preferably polymerized by irradiation with ultraviolet light or the like in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for polymerization, suitable types of the initiator and suitable amounts thereof are known to those skilled in the art and are described in literatures. For example, Irgacure 651 (registered trade name; BASF), Irgacure 184 (registered trade name; BASF) or Darocure 1173 (registered trade name; BASF), each being a photoinitiator, is suitable for radical polymerization. A preferred ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight of the polymerizable compound, and a particularly preferred ratio is in the range of approximately 1% by weight to approximately 3% by weight.

Seventh, the methods for synthesizing the component compounds will be explained. Compound (1) to compound (4) can be prepared by a known method. Examples of synthetic methods will be shown. Compound (2-1) is prepared by the method described in JP S59-176221 A. Compound (3-3-1), compound (3-6-2), compound (3-7-1) and compound (3-10-1) are prepared by the method described in JP H10-251186 A. Compound (3-14-1) and compound (3-16-1) are prepared by the method described in JP H2-233626 A. Compound (4-4-1) is prepared by the method described in JP S57-165328 A and JP S59-176221 A. The antioxidant is commercially available. A compound represented by formula (6) where q is 1 is available from Sigma-Aldrich Corporation. Compound (6) where q is 7 and so forth are prepared according to the method described in U.S. Pat. No. 3,660,505 B.

Any compounds whose synthetic methods are not described above can be prepared according to the methods described in books such as Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Shin Jikken Kagaku Koza in Japanese) (Maruzen Co., Ltd.). The composition is prepared according to publicly known methods using the thus obtained compounds. For example, the component compounds are mixed and dissolved in each other by heating.

Last, the application of the composition will be explained. The composition of the invention mainly has a minimum temperature of approximately −10° C. or lower, a maximum temperature of approximately 70° C. or higher, and an optical anisotropy in the range of approximately 0.07 to approximately 0.20. A device including the composition has a large voltage holding ratio. The composition is suitable for use in the AM device. The composition is particularly suitable for use in a transmissive AM device. The composition having an optical anisotropy in the range of approximately 0.08 to approximately 0.25, and also the composition having an optical anisotropy in the range of approximately 0.10 to approximately 0.30 may be prepared by controlling the ratio of the component compounds or by mixing with any other liquid crystal compound. The composition can be used as a composition having the nematic phase, and as the optically active composition by adding the optically active compound.

The composition can be used for the AM device. The composition can also be used for a PM device. The composition can also be used for an AM device and a PM device both having a mode such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, PSA or FPA. Use for an AM device having the TN, OCB, IPS or FFS mode is particularly preferred. In an AM device having the IPS mode or the FFS mode, alignment of liquid crystal molecules in a state in which no voltage is applied may be parallel or perpendicular relative to a panel substrate. The devices may be of a reflective type, a transmissive type or a transflective type. Use for the transmissive device is preferred. The composition can also be used for an amorphous silicon-TFT device or a polycrystal silicon-TFT device. The composition can also be used for a nematic curvilinear aligned phase (NCAP) device prepared by microencapsulating the composition, and for a polymer dispersed (PD) device in which a three-dimensional network-polymer is formed in the composition.

It will be apparent to those skilled in the art that various modifications and variations can be made in the invention and specific examples provided herein without departing from the spirit or scope of the invention. Thus, it is intended that the invention covers the modifications and variations of this invention that come within the scope of any claims and their equivalents.

The following examples are for illustrative purposes only and are not intended, nor should they be interpreted to, limit the scope of the invention.

EXAMPLES

In order to evaluate characteristics of a composition and a compound to be contained in the composition, the composition and the compound were made a measurement object. When the measurement object was a composition, the composition was measured as was as a sample, and values obtained were described. When the measurement object was a compound, a sample for measurement was prepared by mixing the compound (15% by weight) with a base liquid crystal (85% by weight). Values of characteristics of the compound were calculated using values obtained by measurement, according to an extrapolation method: (extrapolated value)={(measured value of a sample for measurement)−0.85×(measured value of a base liquid crystal)}/0.15. When a smectic phase (or crystals) precipitated at the ratio thereof at approximately 25° C., a ratio of the compound to the base liquid crystal was changed step by step in the order of (10% by weight:90% by weight), (5% by weight:95% by weight) and (1% by weight:99% by weight). Values of a maximum temperature, optical anisotropy, viscosity and dielectric anisotropy with regard to the compound were obtained according to the extrapolation method.

Components of the base liquid crystal were as described below. A ratio of each component is expressed in terms of % by weight.

Characteristics were measured according to the methods described below. Most of the methods are applied as described in the Standard of Japan Electronics and Information Technology Industries Association (hereinafter, abbreviated as JEITA) discussed and established as the Standard of JEITA (JEITA ED-2521B), or as modified thereon.

Maximum Temperature of a Nematic Phase (NI; ° C.):

A sample was placed on a hot plate in a melting point apparatus equipped with a polarizing microscope and was heated at a rate of 1° C. per minute. Temperature at which part of the sample began to change from a nematic phase to an isotropic liquid was measured. A higher limit of a temperature range of the nematic phase may be occasionally abbreviated as “maximum temperature.”

Minimum Temperature of a Nematic Phase (T_(c); ° C.):

Samples each having a nematic phase were put in glass vials and kept in freezers at temperatures of 0° C., −10° C., −20° C., −30° C. and −40° C. for 10 days, and then liquid crystal phases were observed. For example, when a sample maintained the nematic phase at −20° C. and changed to crystals or a smectic phase at −30° C., T_(c) was expressed as T_(c)<−20° C. A lower limit of the temperature range of the nematic phase may be occasionally abbreviated as “minimum temperature.”

Viscosity (Bulk Viscosity; η; Measured at 20° C.; mPa·s):

A cone-plate (E type) rotational viscometer was used for measurement.

Viscosity (Rotational Viscosity; γ1; Measured at 25° C.; mPa·s):

Measurement was carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample was put in a TN device in which a twist angle was 0 degrees and a distance (cell gap) between two glass substrates was 5 micrometers. Voltage was stepwise applied to the device in the range of 16 V to 19.5 V at an increment of 0.5 V. After a period of 0.2 second with no application, voltage was applied repeatedly under the conditions of only one of rectangular waves (rectangular pulse; 0.2 second) and no application (2 seconds). A peak current and a peak time of a transient current generated by the application were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) on page 40 of the paper presented by M. Imai et al. A value of dielectric anisotropy necessary for the calculation was determined according to the method as described below by using the device used for measuring the rotational viscosity.

Optical Anisotropy (Refractive Index Anisotropy; Δn; Measured at 25° C.):

Measurement was carried out by means of Abbe refractometer with a polarizing plate mounted on an ocular, using light at a wavelength of 589 nanometers. A surface of a main prism was rubbed in one direction, and then a sample was added dropwise onto the main prism. A refractive index (n∥) was measured when the direction of polarized light was parallel to the direction of rubbing. A refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. A value of optical anisotropy was calculated from an equation: Δn=n∥−n⊥.

Dielectric Anisotropy (Δ∈; Measured at 25° C.):

A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 micrometers and a twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant (∈∥) in the major axis direction of liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant (∈⊥) in the minor axis direction of the liquid crystal molecules was measured. A value of dielectric anisotropy was calculated from an equation: Δ∈=∈∥−∈⊥.

Threshold Voltage (Vth; Measured at 25° C.; V):

An LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used for measurement. A light source was a halogen lamp. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 0.45/Δn (μm) and a twist angle was 80 degrees. A voltage (32 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 10 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is a voltage at 90% transmittance.

Voltage Holding Ratio (VHR-1; Measured at 25° C.; %):

A TN device used for measurement had a polyimide alignment film, and a distance (cell gap) between two glass substrates was 5 micrometers. A sample was put in the device, and then the device was sealed with an ultraviolet-curable adhesive. A pulse voltage (60 microseconds at 5 V) was applied to the device and the device was charged. A decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is a percentage of area A to area B.

Voltage Holding Ratio (VHR-2; Measured at 80° C.; %):

A TN device used for measurement had a polyimide alignment film, and a distance (cell gap) between two glass substrates was 5 micrometers. A sample was put in the device, and then the device was sealed with an ultraviolet-curable adhesive. A pulse voltage (60 microseconds at 5 V) was applied to the TN device and the device was charged. A decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is a percentage of area A to area B.

Voltage Holding Ratio (VHR-3; Measured at 25° C.; %):

Stability to ultraviolet light was evaluated by measuring a voltage holding ratio after a device was irradiated with ultraviolet light. A TN device used for measurement had a polyimide alignment film, and a cell gap was 5 micrometers. A sample was injected into the device, and then the device was irradiated with ultraviolet light for 20 minutes. A light source was an ultra high-pressure mercury lamp USH-500D (made by Ushio, Inc.), and a distance between the device and the light source was 20 centimeters. In measuring VHR-3, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-3 has a large stability to ultraviolet light. A value of VHR-3 is preferably 90% or more, further preferably, 95% or more.

Voltage Holding Ratio (VHR-4; Measured at 25° C.; %):

A TN device into which a sample was injected was heated in a constant-temperature bath at 80° C. for 500 hours, and then stability to heat was evaluated by measuring a voltage holding ratio. In measuring VHR-4, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

Response Time (τ; Measured at 25° C.; ms):

An LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used for measurement. A light source was a halogen lamp. A low-pass filter was set at 5 kHz. A sample was put in a normally white mode TA device in which a distance (cell gap) between two glass substrates was 5.0 micrometers and a twist angle was 80 degrees. Rectangular waves (60 Hz, 5 V, 0.5 second) were applied to the device. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and the amount of light transmitted through the device was measured. The maximum amount of light corresponds to 100% transmittance, and the minimum amount of light corresponds to 0% transmittance. Rise time (τr:ms) is a period of time required for a change of transmittance from 90% to 10%. Fall time (τf:ms) is a period of time required for a change of transmittance from 10% to 90%. The response time is a sum of the thus obtained rise time and fall time.

Elastic Constant (K; Measured at 25° C.; pN):

HP4284A LCR Meter made by Yokogawa-Hewlett-Packard Co. was used for measurement. A sample was put in a horizontal alignment cell in which a distance (cell gap) between two glass substrates was 20 micrometers. Voltage in the range of 0 V to 20 V was applied to the cell, and electrostatic capacity and applied voltage were measured. Measured values of the electrostatic capacity (C) and the applied voltage (V) were fitted to equation (2. 98) and equation (2. 101) on page 75 of “Liquid Crystal Device Handbook” (Ekisho Debaisu Handobukku in Japanese) (The Nikkan Kogyo Shimbun, Ltd.), and values of K11 and K33 were obtained from equation (2. 99). Next, K22 was calculated using the previously determined values of K11 and K33 in equation (3. 18) on page 171 of the same Handbook. An elastic constant is a mean value of the thus determined K11, K22 and K33.

Specific Resistance (ρ; Measured at 25° C.; Ωcm):

Into a vessel equipped with electrodes, 1.0 milliliter of a sample was injected. A DC voltage (10 V) was applied to the vessel, and a DC current after 10 seconds was measured. A specific resistance was calculated from the following equation: (specific resistance)={(voltage)×(electric capacity of a vessel)}/{(direct current)×(dielectric constant of vacuum)}.

Helical Pitch (P; Measured at Room Temperature; μm):

A helical pitch was measured according to a wedge method (Handbook of Liquid Crystals (Ekisho Binran in Japanese), page 196, (issued in 2000, Maruzen Co., Ltd.)). A sample was injected into a wedge cell and left to stand at room temperature for 2 hours, and then a distance (d2-d1) between disclination lines was observed by means of a polarizing microscope (trade name: MM40/60 Series, Nikon Corporation). A helical pitch (P) was calculated according to the following equation, in which an angle of the wedge cell was expressed as θ: P=2×(d2−d1)×tan θ.

Gas Chromatographic Analysis:

GC-14B Gas Chromatograph made by Shimadzu Corporation was used for measurement. A carrier gas was helium (2 mL per minute). A sample injector and a detector (FID) were set to 280° C. and 300° C., respectively. A capillary column DB-1 (length 30 m, bore 0.32 mm, film thickness 0.25 μm; dimethylpolysiloxane as a stationary phase, non-polar) made by Agilent Technologies, Inc. was used for separation of component compounds. After the column was kept at 200° C. for 2 minutes, the column was heated to 280° C. at a rate of 5° C. per minute. A sample was prepared in an acetone solution (0.1% by weight), and then 1 microliter of the solution was injected into the sample injector. A recorder was C-R5A Chromatopac made by Shimadzu Corporation or the equivalent thereof. The resulting chromatogram showed a peak retention time and a peak area corresponding to each of the component compounds.

As a solvent for diluting the sample, chloroform, hexane and so forth may also be used. The following capillary columns may also be used for separating the component compounds: HP-1 (length 30 m, bore 0.32 mm, film thickness 0.25 μm) made by Agilent Technologies, Inc., Rtx-1 (length 30 m, bore 0.32 mm, film thickness 0.25 μm) made by Restek Corporation and BP-1 (length 30 m, bore 0.32 mm, film thickness 0.25 μm) made by SGE International Pty. Ltd. A capillary column CBP1-M50-025 (length 50 m, bore 0.25 mm, film thickness 0.25 μm) made by Shimadzu Corporation may also be used for the purpose of avoiding an overlap of compound peaks.

A ratio of liquid crystal compounds contained in the composition may be calculated by the method as described below. The liquid crystal compounds can be detected by means of a gas chromatograph. A ratio of the peak areas in the gas chromatogram corresponds to a ratio (in the number of moles) of the liquid crystal compounds. When the capillary columns described above were used, a correction coefficient of each of the liquid crystal compounds may be regarded as 1 (one). Accordingly, a ratio (% by weight) of the liquid crystal compounds was calculated from the ratio of the peak areas.

The invention will be explained in detail by way of Examples. The invention is not limited by the Examples described below. The compounds in Comparative Examples and Examples were described using symbols according to definitions in Table 3 below. In Table 3, a configuration of 1,4-cyclohexylene is trans. A parenthesized number next to a symbolized compound corresponds to the number of the compound. A symbol (−) means any other liquid crystal compound. A ratio (percentage) of the liquid crystal compounds is expressed in terms of weight percent (% by weight) based on the total weight of the liquid crystal composition. The liquid crystal composition includes an impurity in addition thereto. Values of characteristics of the composition were summarized in the last part.

Symbol 1) Left-terminal Group R— C_(n)H_(2n+1)— n- C_(n)H_(2n+1)O— nO- C_(m)H_(2m+1)OC_(n)H_(2n)— mOn- CH₂═CH— V- C_(n)H_(2n+1)—CH═CH— nV- CH₂═CH—C_(n)H_(2n)— Vn- C_(m)H_(2m+1)—CH═CH—C_(n)H_(2n)— mVn- CF₂═CH— VFF- CF₂═CH—C_(n)H_(2n)— VFFn- 2) Right-terminal Group — —C_(n)H_(2n+1) -n —OC_(n)H_(2n+1) -On —CH═CH₂ -V —CH═CH—C_(n)H_(2n+1) -Vn —C_(n)H_(2n)—CH═CH₂ -nV —C_(m)H_(2m)—CH═CH—C_(n)H_(2n+1) -mVn —CH═CF₂ -VFF —F -F —Cl -CL —OCF₃ -OCF3 —CF₃ -CF3 —CF═CH—CF₃ -FVCF3 —CF═CF—CF₃ -FVFCF3 3) Bonding Group —Z_(n)— —C₂H₄— 2 —COO— E —CH═CH— V —CH₂O— 1O —OCH₂— O1 —CF₂O— X —C≡C— T 4) Ring Structure —A_(n)—

H

B

B(F)

B(2F)

B(F,F)

B(2F,5F)

Py

G

dh 5) Examples of Description Example 1 3-HH-FVCF3

Example 2 3-BB(F)B(F,F)XB(F,F)-F

Example 1

3-HH-FVCF3 (1-1-1) 5% 3-HH-V (2-1) 43% 4-GB(F)B(F,F)XB(F,F)-F (3-8-1) 4% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-HB-CL (3-12-1) 7% 3-BB(F)B(F,F)-F (3-17-1) 3% V2-BB-1 (4-2-1) 3% V-HHB-1 (4-4-1) 12% V2-HHB-1 (4-4-1) 4% 2-BB(F)B-3 (4-7-1) 4% 1-BB(F)B-2V (4-7-1) 4% 3-HHEBH-3 (4-8-1) 5% NI = 77.1° C.; Tc < −20° C.; η = 13.6 mPa · s; Δn = 0.098; Δε = 3.6; Vth = 2.02 V.

Comparative Example 1

A composition was formulated in which compound (1-1-1) being a first component of the present invention was replaced by a compound that was similar thereto and described in Composition Example of JP 2005-298466 A in the composition in Example 1. The composition was prepared and measured by the method mentioned above. Components and characteristics of the composition are as described below.

3-HH-FVFCF3 (1-1-1)-like 5% 3-HH-V (2-1) 43% 4-GB(F)B(F,F)XB(F,F)-F (3-8-1) 4% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-HB-CL (3-12-1) 7% 3-BB(F)B(F,F)-F (3-17-1) 3% V2-BB-1 (4-2-1) 3% V-HHB-1 (4-4-1) 12% V2-HHB-1 (4-4-1) 4% 2-BB(F)B-3 (4-7-1) 4% 1-BB(F)B-2V (4-7-1) 4% 3-HHEBH-3 (4-8-1) 5% NI = 77.4° C.; Tc < −10° C.; η = 13.3 mPa · s; Δn = 0.099; Δε = 3.1; Vth = 2.11 V.

The composition in Comparative Example 1 has a smaller dielectric anisotropy and a higher minimum temperature in comparison with the composition in Example 1.

Example 2

3-HH-FVCF3 (1-1-1) 4% 5-HH-FVCF3 (1-1-1) 3% 3-HH-V (2-1) 45% 3-HH-V1 (2-1) 5% 3-GB(F,F)XB(F,F)-F (3-4-1) 5% 3-HBBXB(F,F)-F (3-6-1) 3% 3-BB(F)B(F,F)XB(F,F)-F (3-10-1) 3% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 8% 3-HHEH-3 (4-3-1) 3% V-HHB-1 (4-4-1) 9% 3-HHB-1 (4-4-1) 3% 3-HHB-3 (4-4-1) 3% 5-HBB(F)B-2 (4-12-1) 6% NI = 86.7° C.; Tc < −20° C.; η = 10.5 mPa · s; Δn = 0.091; Δε = 4.0; Vth = 1.98 V.

Example 3

3-HH-FVCF3 (1-1-1) 3% 3-HHVH-FVCF3 (1-3-1) 3% 3-HH-V (2-1) 25% 5-HH-V (2-1) 4% 3-BBXB(F,F)-F (3-2-1) 5% 3-BB(F,F)XB(F,F)-F (3-3-1) 9% 3-HHXB(F,F)-F (3-5-1) 16% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-BB(F,F)XB(F)B(F,F)-F (3-11-1) 4% 3-HHB(F,F)-F (3-13-1) 3% 3-HBB(F,F)-F (3-14-1) 5% 2-HHBB(F,F)-F (3-18-1) 3% V-HHB-1 (4-4-1) 10% V2-HHB-1 (4-4-1) 4% NI = 82.3° C.; Tc < −20° C.; η = 11.7 mPa · s; Δn = 0.100; Δε = 8.6; Vth = 1.45 V.

Example 4

3-HH-FVCF3 (1-1-1) 4% 3-BHH-FVCF3 (1-2-1) 5% 5-BHH-FVCF3 (1-2-1) 3% 3-HH-V (2-1) 39% 3-HH-V1 (2-1) 10% 3-BB(F,F)XB(F,F)-F (3-3-1) 3% 3-BB(F)B(F,F)XB(F,F)-F (3-10-1) 3% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 5% 3-HHB(F)-F (3-13) 3% 3-HHBB(F,F)-F (3-18-1) 4% 4-HHBB(F,F)-F (3-18-1) 3% V-HHB-1 (4-4-1) 12% V2-HHB-1 (4-4-1) 3% 5-HBB-2 (4-5-1) 3% NI = 91.7° C.; Tc < −20° C.; η = 13.0 mPa · s; Δn = 0.088; Δε = 4.0; Vth = 2.01 V.

Example 5

5-HH-FVCF3 (1-1-1) 3% 3-BHH-FVCF3 (1-2-1) 6% 3-HH-V (2-1) 25% 4-HH-V1 (2-1) 3% 3-HH-VFF (2-1) 3% 5-HXB(F,F)-F (3-1-1) 3% 1-HHXB(F,F)-F (3-5-1) 6% 3-HHXB(F,F)-F (3-5-1) 12% 3-HBB(F,F)XB(F,F)-F (3-6-2) 3% 3-HHB(F,F)XB(F,F)-F (3-7-1) 5% 3-BB(F)B(F,F)XB(F)-F (3-10-2) 3% 3-HB-CL (3-12-1) 4% 3-HHB(F,F)-F (3-13-1) 5% 3-HHB-CL (3-13-2) 3% 3-HHEB(F,F)-F (3-16-1) 3% 3-BB(F)B(F,F)-CF3 (3-17-2) 3% 1-BB-3 (4-2-1) 4% 5-HBBH-3 (4-10-1) 3% 3-HB(F)BH-3 (4-11-1) 3% NI = 81.6° C.; Tc < −30° C.; η = 13.2 mPa · s; Δn = 0.086; Δε = 6.5; Vth = 1.39 V.

Example 6

3-HH-FVCF3 (1-1-1) 3% 5-BHH-FVCF3 (1-2-1) 3% 4-HH-V (2-1) 12% 3-HH-2V1 (2-1) 3% 3-BB(F,F)XB(F,F)-F (3-3-1) 10% 3-BB(F,F)XB(F)-OCF3 (3-3-2) 4% 3-HHXB(F,F)-F (3-5-1) 10% 3-HHXB(F,F)-CF3 (3-5-2) 4% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-GHB(F,F)-F (3-15-1) 3% 7-HB-1 (4-1-1) 6% 3-HB-O2 (4-1-1) 9% V-HHB-1 (4-4-1) 16% V2-HHB-1 (4-4-1) 5% 3-HHB-O1 (4-4-1) 3% 3-HB(F)HH-5 (4-9-1) 3% NI = 81.8° C.; Tc < −30° C.; η = 18.4 mPa · s; Δn = 0.096; Δε = 5.9; Vth = 1.70 V.

Example 7

3-HH-FVCF3 (1-1-1) 4% 3-BHH-FVCF3 (1-2-1) 4% 3-HH-V (2-1) 41% 3-HH-V1 (2-1) 10% 5-HBBXB(F,F)-F (3-6-1) 3% 3-BB(F)B(F,F)XB(F,F)-F (3-10-1) 3% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-HHB(F)-F (3-13) 3% 3-HHBB(F,F)-F (3-18-1) 4% 4-HHBB(F,F)-F (3-18-1) 3% V-HHB-1 (4-4-1) 13% 5-HBB-2 (4-5-1) 3% 5-B(F)BB-2 (4-6-1) 3% NI = 94.1° C.; Tc < −20° C.; η = 12.0 mPa · s; Δn = 0.093; Δε = 3.4; Vth = 2.22 V.

Example 8

3-HH-FVCF3 (1-1-1) 5% 3-HH-V (2-1) 22% 3-BBXB(F,F)-F (3-2-1) 5% 3-BB(F,F)XB(F,F)-F (3-3-1) 9% 3-HHXB(F,F)-F (3-5-1) 16% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-BB(F,F)XB(F)B(F,F)-F (3-11-1) 4% 3-HHB(F,F)-F (3-13-1) 3% 3-HBB(F,F)-F (3-14-1) 5% 2-HHBB(F,F)-F (3-18-1) 4% V-HHB-1 (4-4-1) 10% V2-HHB-1 (4-4-1) 4% 3-HH-4 (—) 4% 3-HH-O1 (—) 3% NI = 78.4° C.; Tc < −20° C.; η = 11.9 mPa · s; Δn = 0.097; Δε = 8.6; Vth = 1.40 V.

Example 9

3-HH-FVCF3 (1-1-1) 5% 3-HH-V (2-1) 22% 3-BBXB(F,F)-F (3-2-1) 5% 3-BB(F,F)XB(F,F)-F (3-3-1) 9% 3-HHXB(F,F)-F (3-5-1) 16% 3-dhBB(F,F)XB(F,F)-F (3-9-1) 3% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-BB(F,F)XB(F)B(F,F)-F (3-11-1) 4% 3-HBB(F,F)-F (3-14-1) 5% 2-HHBB(F,F)-F (3-18-1) 4% V-HHB-1 (4-4-1) 10% V2-HHB-1 (4-4-1) 4% 3-HH-4 (—) 4% 3-HH-O1 (—) 3% NI = 79.2° C.; Tc < −20° C.; η = 13.3 mPa · s; Δn = 0.100; Δε = 8.7; Vth = 1.40 V.

Example 10

V-HH-FVCF3 (1-1-1) 5% 3-HH-V (2-1) 22% 3-BBXB(F,F)-F (3-2-1) 5% 3-BB(F,F)XB(F,F)-F (3-3-1) 9% 3-HHXB(F,F)-F (3-5-1) 16% 3-dhBB(F,F)XB(F,F)-F (3-9-1) 3% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-BB(F,F)XB(F)B(F,F)-F (3-11-1) 4% 3-HBB(F,F)-F (3-14-1) 5% 2-HHBB(F,F)-F (3-18-1) 4% V-HHB-1 (4-4-1) 10% V2-HHB-1 (4-4-1) 4% 3-HH-4 (—) 4% 3-HH-O1 (—) 3% NI = 78.2° C.; Tc < −20° C.; η = 13.2 mPa · s; Δn = 0.100; Δε = 8.6; Vth = 1.40 V.

Example 11

1V-HH-FVCF3 (1-1-1) 3% 5-BHH-FVCF3 (1-2-1) 3% 4-HH-V (2-1) 12% 3-HH-2V1 (2-1) 3% 3-BB(F,F)XB(F,F)-F (3-3-1) 10% 3-BB(F,F)XB(F)-OCF3 (3-3-2) 4% 3-HHXB(F,F)-F (3-5-1) 10% 3-HHXB(F,F)-CF3 (3-5-2) 4% 4-BB(F)B(F,F)XB(F,F)-F (3-10-1) 6% 3-GHB(F,F)-F (3-15-1) 3% 7-HB-1 (4-1-1) 6% 3-HB-O2 (4-1-1) 9% V-HHB-1 (4-4-1) 16% V2-HHB-1 (4-4-1) 5% 3-HHB-O1 (4-4-1) 3% 3-HB(F)HH-5 (4-9-1) 3% NI = 82.2° C.; Tc < −30° C.; η = 18.5 mPa · s; Δn = 0.097; Δε = 6.0; Vth = 1.69 V.

The compositions in Example 1 to Example 11 have a larger dielectric anisotropy and a lower minimum temperature in comparison with the composition in Comparative Example 1. Therefore, the liquid crystal composition of the present invention has superb characteristics.

Although the invention has been described and illustrated with a certain degree of particularity, it is understood that the disclosure has been made only by way of example, and that numerous changes in the conditions and order of steps can be resorted to by those skilled in the art without departing from the spirit and scope of the invention.

INDUSTRIAL APPLICABILITY

The invention concerns a liquid crystal composition satisfying at least one of characteristics such as a high maximum temperature of a nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a large specific resistance, a large elastic constant, a high stability to ultraviolet light and a high stability to heat, or a liquid crystal composition having a suitable balance regarding at least two of the characteristics. A liquid crystal display device including such a composition is applied to constitute an AM device having a short response time, a large voltage holding ratio, a large contrast ratio, a long service life and so forth, and thus can be used for a liquid crystal projector, a liquid crystal television and so forth. 

What is claimed is:
 1. A liquid crystal composition that has a nematic phase and contains at least one compound selected from the group of compounds represented by formula (1) as a first component and at least one compound selected from the group of compounds represented by formula (2) as a second component:

wherein, R¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine; R² is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; R³ is alkenyl having 2 to 12 carbons, or —CH═CF₂; ring A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; ring B is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z¹ is independently a single bond, ethylene, vinylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; and m is 1, 2 or
 3. 2. The liquid crystal composition according to claim 1, containing at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-3) as the first component:

wherein, R¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine.
 3. The liquid crystal composition according to claim 1, wherein a ratio of the first component is in the range of 5% by weight to 30% by weight and a ratio of the second component is in the range of 10% by weight to 95% by weight, based on the total weight of the liquid crystal composition.
 4. The liquid crystal composition according to claim 1, further containing at least one compound selected from the group of compounds represented by formula (3) as a third component:

wherein, R⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring C is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; X¹ and X² are independently hydrogen or fluorine; Y¹ is fluorine, chlorine, trifluoromethyl or trifluoromethoxy; Z² is independently a single bond, ethylene, carbonyloxy or difluoromethyleneoxy; and n is 1, 2 or
 3. 5. The liquid crystal composition according to claim 4, containing at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-18) as the third component:

wherein, R⁴ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; X¹, X², X³, X⁴, X⁵, X⁶, X⁷ and X⁸ are independently hydrogen or fluorine; and Y¹ is fluorine, chlorine, trifluoromethyl or trifluoromethoxy.
 6. The liquid crystal composition according to claim 4, wherein a ratio of the third component is in the range of 10% by weight to 85% by weight based on the total weight of the liquid crystal composition.
 7. The liquid crystal composition according to claim 1, further containing at least one compound selected from the group of compounds represented by formula (4) as a fourth component:

wherein, R⁵ and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine; ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene; Z³ is independently a single bond, ethylene or carbonyloxy; p is 1, 2 or 3; and ring E when p is 1 is 1,4-phenylene.
 8. The liquid crystal composition according to claim 4, further containing at least one compound selected from the group of compounds represented by formula (4) as a fourth component:

wherein, R⁵ and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine; ring D and ring E are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene; Z³ is independently a single bond, ethylene or carbonyloxy; p is 1, 2 or 3; and ring E when p is 1 is 1,4-phenylene.
 9. The liquid crystal composition according to claim 7, containing at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-12) as the fourth component:

wherein, R⁵ and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine.
 10. The liquid crystal composition according to claim 8, containing at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-12) as the fourth component:

wherein, R⁵ and R⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one of hydrogen is replaced by fluorine.
 11. The liquid crystal composition according to claim 7, wherein a ratio of the fourth component is in the range of 5% by weight to 75% by weight based on the total weight of the liquid crystal composition.
 12. The liquid crystal composition according to claim 8, wherein a ratio of the fourth component is in the range of 5% by weight to 75% by weight based on the total weight of the liquid crystal composition.
 13. The liquid crystal composition according to claim 1, wherein a maximum temperature of a nematic phase is 70° C. or higher, an optical anisotropy (25° C.) at a wavelength of 589 nanometers is 0.07 or more, and a dielectric anisotropy (25° C.) at a frequency of 1 kHz is 2 or more.
 14. A liquid crystal display device including the liquid crystal composition according to claim
 1. 15. The liquid crystal display device according to claim 14, wherein an operating mode in the liquid crystal display device is a TN mode, an ECB mode, an OCB mode, an IPS mode, a PSA mode or an FPA mode, and a driving mode in the liquid crystal display device is an active matrix mode. 